Sulphamic acid salts of polymeric amino compounds



Patented May 21, 1940 UNITED STATES PATENT OFFICE SULPHAMIC ACID SALTSOF POLYMERIC AMINO COMPOUNDS No Drawing. Application May 27, 1938.

Serial No. 210,531

7 Claims.

This invention relates to new compositions of matter and moreparticularly to.compositions of matter obtainable by reacting sulphamicacid with polymeric amino nitrogen containing substances soluble in 5%aqueous acetic acid, insoluble in water and 5% aqueous ammonia, andcapable of being formed into a coherent film.

This invention has as an object the preparation of new compounds. Afurther object is the preparation of new emulsifying, dispersing,sizing, thickening and adhesive agents. Other objects will appearhereinafter.

These objects are accomplished by the following invention whereinsulphamic acid is reacted, preferably in aqueous solution, with apolymeric amino nitrogen containing substance soluble in 5% aqueousacetic acid, insoluble in water and 5% aqueous ammonia, and capable ofbeing formed.

into a coherent film.

In one mode of the practice of the invention, the polymeric aminonitrogen containing substance, hereinafter called the amino polymer, isstirred with a solution, preferably aqueous, of sulphamic acid. Thesolution thus made is frequently used without isolation of the compoundor reaction product which may, however, be isolated by appropriateprocedures as given in detail below.

The more detailed practice of the invention is illustrated by thefollowing examples. Parts given are by weight. There are of course manyforms of the invention other than these specific embodiments.

Example I Twenty (20) parts of medium viscosity partially deacetylatedchitin, prepared according to the procedure outlined in Rigby U. S. P.2,040,879, was stirred into 460 parts of water containing 20 parts ofsulphamic acid. After stirring for 15 minutes a clear homogeneoussolution of the sulphamic acid derivative of the partially deacetylatedchitin was obtained. This solution, which had a viscosity of about 15poises at 25 C.,- was slowly poured with stirring into 2000 parts ofmethanol and allowed to stand for about one hour. The precipitatedcompound of sulphamic acid and partially deacetlyated chitin wasseparated by filtration and dried in an oven at C. for 2 hours. Thefinal product was a dry powder which was non-hygroscopic on exposure toa humid atmosphere and which was readily redissolved in water.

Attempts to prepare similarly the solid acetic acid derivative of thesame deacetylated chitin were not successful. A gel-like mass formedupon addition of the reaction mixture to methanol. Moreover, acetic acidwas volatilized during the drying operation at 70 C., thereby renderingthe final product insoluble in water. The corresponding sulphuric acidderivative made from the same partially deacetylated chitin was found tobe entirely insoluble in water.

Upon heating the dry sulphamic acid derivative of partially deacetylatedchitin, preferably in an inert atmosphere of nitrogen, at Mil-160 C. forone-fourth to one hour, a product soluble in dilute alkali as well as inwater is obtained.

Solutions of the sulphamic acid-partially de acetylated chitin reactionproducts show delayed precipitation of the insoluble sulphuric acidderivatives of deacetylated chitin when solutions containing sulphateion are added, a period of 3 to 24 hours being generally required beforeprecipitation begins to take place. On the other hand, under similarconditions, immediate precipitation of the insoluble sulphuric acidderivatives of partially deacetylated chitin occurs when a solublesulphate in solution is added to an aqueous solution of the acetic acidderivative of the deacetylated chitin.

There may be used in Example I with good results, any of the grades ofdeacetylated chitin described in U. S. 2,040,879.

Example II Eight (8) parts of phenol-formaldehyde-methylamine resinprepared by the method described in Example I of U. S. Patent 2,098,869,was dissolved in 92 parts of 2% aqueous sulphamic acid. The resultingsolution had a viscosity of about 10 poises at 25 C. A film obtained byevaporation of the solution on a glass plate was clear and transparent.

In place of the above resin, any other primary amine-phenol-aldehyderesinssuch as those disclosed in U. S. Patent 2,098,869 may be used withlike results.

Example III Eight (8) parts of phenol-formaldehyde-dimethylamine resinprepared by the method disclosed in Example I of U. S. Patent 2,031,557,was dissolved in 92 parts of 5% aqueous sulphamic acid forming a clear,transparent solution. Such solutions showed high surface activeproperties and foamed strongly when shaken. A clear film of theresin-sulphamic acid reaction product was obtained by drying thesolution flowed upon a glass plate. Heating the film at C. for one hourlowered its solubility in water so that it was only slightly soluble.

In place of the above resin, any of the other secondaryamine-phenol-aldehyde resins of U. S. 2,031,557 may be similarlyconverted into compounds of sulphamic acid. In general, such compoundsshow high solubility in water, and the resulting solutions at equivalentconcentrations have a lower viscosity than analogous solutions of thecorresponding compounds of other inorganic acids. These reactionproducts of sulphamic acid with amine-phenol-aldehyde' resins also showbetter heat resistance and storage stability than correspondingcompounds of organic acids such as formic, acetic and propionic acids.

Example IV To 90 parts of 0.5% aqueous sulphamic acid solution was addedwith stirring 10 parts of diethylaminomethylzein which was preparedaccording to the method described in Example IV of Meigs copendingapplication, Serial No. 59,643, filed January 17, 1936 Patent No.2,143,023. The zein derivative readily dissolved to form a clear,viscous solution. A film of the solid sulphamicacid-diethylaminomethylzein reaction product was obtained uponevaporating a layer of the solution placed upon a glass plate. Heatingthe film in an oven at 100 C. for 1 to 2 hours did not insolubilize thefilm.

Solutions of the above diethylaminomethylzein sulphamic acid reactionproduct show good foaming properties even in the presence of calciumsalts. On the other hand, the sulphuric acid derivative ofdiethylaminomethylzein, similarly prepared shows low solubility and poorsurface active properties in the presence of ordinary hard water" salts.

In place of the above-mentioned zein derivative, any of the otheracid-soluble resinous reaction products of a protein, an amine of lessthan nine carbon atoms and a lower aliphatic aldehyde or ketone,disclosed in Meigs copending application, Serial No. 59,643, filedJanuary 17, 1936, may be used with like result and with advantagesanalogous to those mentioned above.

Example V To 90 parts of 2% aqueous sulphamic acid solution was addedwith stirring 10 parts of polymeric beta-diethylaminoethyl methacrylatewhich had been prepared and polymerized as described in Example II ofHarmon copending application, Serial No. 21,810, filed May 16, 1935Patent No. 2,138,762. The resulting solution was clear and transparent,had a viscosity of about 5 poises at 25 C. and showed moderate foamingand surface active properties. Upon removal of the excess sulphamic acidby addition of sodium nitrate, the solution showed greatly improvedfoaming properties. No precipitation took place even upon the additionof a large excess of sodium nitrite to the solution. The nitrogenliberated by reaction of sodium nitrite with sulphamic acid causedextensive foaming of the solution.

A cotton broadcloth fabric impregnated with about 1% of the abovesulphamic acid compound, of polymeric diethylaminoethyl methacrylateshowed a definite sizing effect. No deleterious effect on the fabric wasnoticeable after heating the treated fabric for 1 hour at 100 C.

Similar sulphamic acid compounds may be readily prepared in like mannerfrom any of the polymeric tertiary amino acrylates and meth-I acrylatesdescribed in Harmon copending application, Serial No. 21.810, filed May16, 1985.

A large variety of polymeric substances which contain basic amino groupsmay be employed for the preparation of sulphamic acid compounds.Generically applicable are polymeric amino nitrogen containingsubstances which are soluble in 5% aqueous acetic acid, insoluble inwater and 5% aqueous ammonia, and capable of being formed into acoherent film. In addition to the types already illustrated in theexamples, the following further classes of such polymeric materials maybe employed: (1) amino polymers derived from reaction of vinyl ketonepolymers with ammonia or primary amines, such as those described inBalthis, Ser. No. 69,725, filed March 19, 1936, Patent No. 2,122,707;(2) polymeric products obtained by the hydrogenation, in the presence ofammonia or amines, of resins containing ketone groups, such as aredescribed in Greenewalt U. S. Patent 2,063,158; (3) amino polymersderived from the reaction of formaldehyde with tertiary aminophenols, e.g., those disclosed in Graves copending application, Serial No. 82,651,filed May 29, 1936, Patent No. 2,147,789; (4) aminocelluloses soluble indilute acetic acid containing an amino nitrogen attached to thecellulose nucleus or separated therefrom by a chain of carbon atoms, forexample, those described in Hardy copending application, Serial No.61,842; filed January 31, 1936, Patent No. 2,136,296, and in Haskinscopending application, Serial No. 61,806, filed January 31, 1936, PatentNo. 2,136,299; (5) polymeric amino-nitrogen containing resins soluble indilute acetic acid, prepared by treating polyvinylchloroacetate withsecondary amines; (6) resins prepared by reacting aliphatic or alicyclicketones with formaldehyde and primary or secondary aliphatic amines; (7)resinous products resulting from the reaction between diphenylor otherdiarylguanidine, formaldehyde and primary or secondary amines; (8)resins prepared by reacting urea and formaldehyde with lower primary orsecondary aliphatic amines; (9) reaction products of epichlorohydrinwith ammonia or primary aliphatic amines, which reaction products havebeen polymerized in the presence of catalytic proportions of stannicchloride; (10) the reaction product of phenollignin with dimethylamineand formaldehyde; (11) the reaction products of triethanolamine withphthalic esters.

Additional examples of specific polymeric amino-nitrogen containingsubstances which function in this invention are as follows:resorcinol-formaldehyde-methylamine resin;phenolformaldehyde-cyclohexylamine resin;phenolformaldehyde-ethylene-diamine resin;xylenolformaldehyde-methylamine resin; phenol-formaldehyde-n-butylamineresin; phenol-formaldehyde-diethylamine resin;phenol-formaldehydedibutylamine resin;phenol-formaldehyde-diethanol-amine resin; dimethylaminopropylcellulose; fi-aminoethoxyethyl cellulose; ,s-dibutylaminoethylcellulose; the mixed aminoethylaminoethoxypropyl ether of cellulose;dibutylaminopropyl cellulose; the mixed methyl dimethylaminopropyl etherof cellulose; amylaminomethyl cellulose; diethylamino glycol cellulose;hydroxyethylamino glycol cellulose; benzylamino methyl cellulose;diethylamino methyl cellulose; 2-hdroxycyclohexylamino methyl cellulose;amylamino cellulose; fl-dicyclohexylaminoethyl methacrylate polymer;fi-di-n-butylaminoethyl methacrylate polymer; p-dimethylwhich wasprepared by aminoethyl methacrylate polymer; triethanolaminemonomethacrylate polymer; 2-(diethylamino) cyclohexyl methacrylatepolymer; 4-(pmethacrylyloxylethyl) morpholine polymer;fl-diethylaminoethyl acrylate polymer; p-dicyclohexylaminoethyl acrylatepolymer; l-(fl-acrylyloxyethyl) piperidine polymer; the resins obtainedby the hydrogenation, in the presence of ammonia, of polymerized bis-,(4-ketocyclohexyl)- dimethylmethane; the resin resulting from thehydrogenation, in the presence of ammonia, of methylenecyclohexanonepolymer; the resin obtained from the hydrogenation, in the presence ofammonia, of polymerized methyl vinyl ketone; the reaction product ofpolymeric methyl a-methylvinyl ketone and aqueous ammonia; the reactionproducts of polymeric methyl vinyl ketone and aqueous ammonia (orcyclohexyiamine, glucamine, ethanolamine, or ethylenediamine);dimethylaminoethylzein; dietylaminoethylzein; dibutylaminoethylzein;cyclohexylaminomethylzein; piperidylmethylzein; piperidylmethylglycinin;dimethylaminomethylgliadin; dimethylaminoethylcasein;monoethylaminomethylzein; meta-diethylaminophenol-forma1dehyde resin;the reaction product of polyvinyl chloroacetate and dibutylamine; theresin obtained by reacting cyclohexanone and formaldehyde withmethylamine; the products obtained by reacting acetone andparaformaidehyde with methyl or butylamine; the resin obtained byreacting diphenylguanidine and formaldehyde with methylamine; and theresins obtained by reacting urea and formaldehyde with methyl-,dimethyl-, butyl-, or dibutylamine.

As shown in the examples, it is in most cases preferable to prepare theamino polymersulphamic acid reaction product by dissolving the polymericamine in a dilute aqueous solution of sulphamic acid. The compound'maythen be isolated by evaporation of the solution or by precipitationthrough the addition of water miscible organic solvents in which theaddition compound is insoluble. An alternative procedure which may beused in certain cases comprises stirring a solution or finely dividedsuspension of the polymeric amine in an organic solvent, such asacetone, ether or alcohols, with a slight excess of sulphamic acid.Methanol is the preferred solvent or medium for such procedure as itwill dissolve approximately 4% by weight of sulphamic acid and give morerapid conversion of the polymeric amine to the desired product. If acrystalline grade of sulphamic acid is used, the excess acid remainingundissolved after conversion of the polymeric amine into the sulphamiccompound may be separated from the compound difierence in flotation, i.e., the heavy crystals of sulphamic acid readily settle to the bottom ofthe suspension while the less dense compound rises to the upper portionthereof and can be readily separated. The amine polymer-sulphamic acidproducts prepared by this solvent method are more easily dried thanthose prepared in water solution. Also, they are obtained in a finelydivided physical form and can be ore readily dissolved in water.

Thes new compounds of sulphamic acid with amino polymers show by theirbehavior that they are different from products obtained similarly byreaction of other acids with amino polymers. Thus the solubility inalkali after heat treatment of the compounds of the amino polymer withsulphamic acid, the lack of an immediate pre-,

cipitation by sulphate iron. and the like, indicate a differentstructure and a different kind of compound.

These new compounds show striking and unexpected advantages overproducts made similarly from amine polymers and other acids.- 5 Thus thesulphamic acid compounds are, in general, more readily isolated anddried with heat to a dry, solid, stable, form without volatilization ofthe acid and loss of solubility by the product. The isolation andpreservation of the dry, solid, sulphamic acid reaction products doesnot involve difficulties arising from hygroscopicity such as arefrequently experienced with analogous derivatives of other acids,especially lactic acid. Further, the amino polymer-sulphamic acidreaction products are superior to those from acetic acid in that thelatter are unstable and readily lose combined acetic acid upon beingheated or upon storage at ordinary temperature for an extended period oftime. p

sulphamic acid compounds of amine polymers in general also showexceedingly high solubility in comparison with the correspondingderivatives of many of the well known organic and inorganic acids. Forexample, amino polymers in many cases form highly insoluble compoundswith acids such as sulphuric acid, boric acid, phosphone acid, oxalicacid, succinic acid, salicyclic acid and the like.

A still further unexpected property of sulphamic acid compounds of aminepolymers is that, in general, they show increased stability towardprecipitation by substances which normally would produce almostinstantaneous precipitation if the corresponding amine compound ofanother acid were used. An illustration of such delayed precipitation isgiven under Example I above. Such delayed precipitation allows the useof the products of the present invention in instances where theanalogous derivative of other acids are totally unsatisfactory becauseof the objectionable precipitation which takes place owing tounavoidable contaminating substances present in compositions orsolutions added to the amine polymer derivative. Sulphamic acidderivatives are therefore superior and frequently are the only compoundswhich can be satisfactorily employed when precipitation must be avoided.

An additional advantage shown by sulphamic acid compounds of the presentinvention is that the sulphamic acid present therein in combined formmay readily be converted into sulphuric acid by simple treatment withnitrous acid or under suitable conditions with a nitrite. That is, anacidified solution of an amine polymer compound of sulphamic acid may betreated, under proper conditions, with a nitrite such as sodium nitrite,whereupon a rapid reaction takes place in which nitrogen is liberatedand the suiphamic acid is converted into sulphuric acid, or into sodiumacid sulphate. Such conversion into the sulphuric acid compound thusallows a controllable change in solubility and the phenomenon may beutilized for breaking emulsions. That is, the highly soluble sulphamicacid-amino polymer reaction product which has been used as anemulsifying agent may be rapidly converted into the insoluble sulphuricacid amino polymer reaction product, which has practically noemulsifying property. The emulsion in such a case is broken down intoits component parts, which may then be separated by simple methods. Suchseparation is frequently dimcult, if not impossible, to obtain in anyother way.

" combination withmolding resins.

these compounds may be used as sizing or coating The sulphamic acidcompounds of amine polymers described in this specification may beemployed for many and varied uses. For example, they may be used asemulsifying or dispersing agents, as thickening agents for increasingthe viscosity of aqueous solutions, as adhesives for paper and wood, asstabilizing agents fo'r'easily oxidizable solutions, insect poisons.fungicides. and various related uses. In addition, they may be used inpreparing formed articles such as films, or molded plastic masses,especially when used in Furthermore,

materials.

The above description and examples are intended to be illustrative only.Any modification of or variation therefrom which conforms to the spiritof the invention is intended to be included within the scope of theclaims.

I claim:

1. A sulphamic acid salt of polymeric amino ni.'. trogen containingsubstance soluble in 5% aqueous acetic acid, insoluble in water and 5%aqueous ammonia, and capable of being formed into a coherent film.

2. A sulphamic acid salt oi a resinous reaction product of a phenol, analdehyde and an aliphatic amine having at least one hydrogen on theamino nitrogen, said resinous reaction product being soluble in 5%aqueous acetic acid, insoluble in water and 5% aqueous ammonia, andcapable of being formed into a coherent film.

3. A sulphamic acid salt of a phenol iormalde hyde methyamine resinsoluble in 5% aqueous acetic acid, insoluble in water and 5% aqueousammonia, and capable of being formed into a coherent fllm. l

4. A sulphamic acid salt of deacetylated chitin.

5. A sulphamic acid salt of a polymeric tertiary amino ester of an acidof the class consisting of acrylic and methacrylic acids.

6. A sulphamic acid salt of a dialkylaminoalkyi ester of an acid of theclass consisting of acrylic and methacrylic acids.

"7. A sulphamic acid salt of beta-diethylaminoethyl methacrylate.

MARTIN ELI CU'PERY.

CERTIFICATE or cones-xenon.- Patent n 2,201,762. i May 21,- 191m.

MARTIN ELI CUPERY.

' It is'hereby certified that-error appears in the printed specificationof the above mmbered patent requiring correction as foilows Page 1,first column, line 148, for "deacetlyated" read -deacety1ated--; page 2,first column, line 61, for "nitrate" read nitrite-;- and second column,line 72, for 2-hdroxycyclohexylamino" read --2-hydroxycyo1ohexylamino-;

page 5, first column, line 1+, for "methacrylyloxylethyl" read,--methacrylyloxyethyl--; lines 20 and 21', for dimethylaminoethylzein;dietylaminoethylnein; dibutjlaminoethylzeim" read--d.imethyle.minomethylzein; diethylaminomethylzein;dibutylaminoniethylzeinrq line 75, for "iron" read -ion--; page 14.,first column, line 22, claim 1, before "polymeric" insert -a-; and thatthe said Letters Patent should be read with this correction therein thatthe same may conform to the record of the case in the Patent Office;

Signed and sealed this 1st da of October, A. 1). 191m.

2 Henry Van Aredale,

(Seal) I Acting Commissioner of Patents.

